EP2615137B2 - Polyvinylchlorid-Zusammensetzung, Rohr, Rinne oder Behälter, Verwendung einer PVC-Zusammensetzung und Verwendung eines Rohrs, einer Rinne oder eines Behälters - Google Patents

Polyvinylchlorid-Zusammensetzung, Rohr, Rinne oder Behälter, Verwendung einer PVC-Zusammensetzung und Verwendung eines Rohrs, einer Rinne oder eines Behälters Download PDF

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Publication number
EP2615137B2
EP2615137B2 EP12000194.6A EP12000194A EP2615137B2 EP 2615137 B2 EP2615137 B2 EP 2615137B2 EP 12000194 A EP12000194 A EP 12000194A EP 2615137 B2 EP2615137 B2 EP 2615137B2
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EP
European Patent Office
Prior art keywords
pvc
kda
composition
pipe
resin component
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EP12000194.6A
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German (de)
English (en)
French (fr)
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EP2615137B1 (de
EP2615137A1 (de
Inventor
Stephan Schüssler
Achim Weiss
Gerhard Wewior
Florian Giersbach
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Georg Fischer Deka GmbH
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Georg Fischer Deka GmbH
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Application filed by Georg Fischer Deka GmbH filed Critical Georg Fischer Deka GmbH
Priority to EP12000194.6A priority Critical patent/EP2615137B2/de
Priority to PCT/EP2013/050081 priority patent/WO2013104562A1/de
Priority to BR112014016177-1A priority patent/BR112014016177B1/pt
Priority to CN201380005272.4A priority patent/CN104169360A/zh
Priority to AU2013209093A priority patent/AU2013209093B2/en
Priority to IN1093KON2014 priority patent/IN2014KN01093A/en
Priority to JP2014551579A priority patent/JP6253594B2/ja
Priority to US14/371,104 priority patent/US20150000782A1/en
Priority to RU2014121333A priority patent/RU2621109C2/ru
Publication of EP2615137A1 publication Critical patent/EP2615137A1/de
Publication of EP2615137B1 publication Critical patent/EP2615137B1/de
Publication of EP2615137B2 publication Critical patent/EP2615137B2/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F16L9/133—Rigid pipes of plastics with or without reinforcement the walls consisting of two layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit

Definitions

  • the invention relates to a polyvinyl chloride (PVC) composition according to the preamble of claim 1, a pipe, a gutter or a container for the passage and / or storage of chemically aggressive substances according to the preamble of claim 4, a use of a polyvinyl chloride (PVC) composition according to Claim 7, a use of a polyvinyl chloride (PVC) composition according to claim 8, and a use of a pipe, a gutter or a container according to claim 9.
  • PVC polyvinyl chloride
  • Polyvinyl chloride (PVC) compositions, pipes, gutters or containers for the passage and / or storage of chemically aggressive substances, as well as uses of polyvinyl chloride compositions are known.
  • PVC Polyvinyl chloride
  • PVC-U unplasticized PVC
  • PVC-C post-chlorinated PVC
  • this material also has serious disadvantages: First, it is significantly more expensive than PVC-U, and it can also be more difficult to weld and / or thermoforming. Processing of PVC-C and installation of components comprising this material is therefore cumbersome and expensive. Especially Weld seams often have to be laboriously and expensive tempered. In addition, the chemical resistance profile of PVC-C due to the mandatory addition of impact modifiers is limited for many applications, especially in the chlorine industry. In particular, the material has inherent lability to contact with strong basic media. Incidentally, the use of PVC-C often seems questionable for cost reasons.
  • thermoplastic inner wall a so-called inliner comprising, for example, PVC-U, PVC-C or PP.
  • This inner wall is laminated and / or reinforced with an outer shell which comprises at least one glass fiber reinforced thermoset resin, GFK.
  • the thermoplastic inliner acts as a chemical-resistant layer, in particular as a corrosion barrier, whereby all mechanical loads are absorbed by the GRP shell.
  • the thermoplastic inliner comprises polyolefins such as polypropylene or polyethylene, PE
  • the connection of the inliner to the GRP casing takes place by melting a glass fleece, in particular a braid made of glass fibers.
  • the thermoplastic inliner comprises PVC-U or PVC-C, it is connected to the GRP shell by at least one adhesive resin.
  • connection of an inline polypropylene comprising a glass fleece to the GRP shell prepares in practice difficulties and makes high demands on the craftsmanship qualification of the processor and its quality assurance.
  • Due to high differences in the thermal expansion of the PP liner and the GRP shell high shear forces in the area of the connection of the GRP shell are at strong and frequent temperature changes, as they occur regularly in the chlorine industry in particular by frequent shutdown and startup of plant parts induced in the PP inliner.
  • a wall thickness of the chemical-resistant inliner is limited to a range of less than 8 mm due to the thermal expansion coefficients, which are typically different by a factor of four, of the inliner and the sheath.
  • PVDF polyvinylidene fluoride
  • the invention is therefore based on the object to provide a PVC composition which does not have the disadvantages mentioned.
  • the composition should be versatile in use, in particular in a comparatively high temperature range with outstanding chemical resistance, in particular alkali resistance.
  • the products mentioned should be inexpensive to produce, have a high thermal stability and high chemical resistance to aggressive substances, such as alkalis.
  • the object of the invention is also to specify uses for a PVC composition, said disadvantages do not occur.
  • the object is achieved by providing a PVC composition having the features of claim 1.
  • the overall composition also has a chlorine content of 56% to 62%.
  • total composition is intended to indicate that the PVC composition may comprise other constituents in addition to the PVC resin.
  • the percentage by weight of chlorine refers to the total composition and not exclusively to its PVC content.
  • PVC resin refers to the polyvinyl chloride component or the PVC portion of the overall composition, wherein the PVC resin itself according to the invention comprises more than one resin component or is formed from more than one resin component.
  • PVC resin component according to the invention comprises polyvinyl chlorides with different chlorine content.
  • the same composition it is possible with the same composition to extrude tubes with an outer diameter up to 600 mm and wall thicknesses in particular of an inliner up to ⁇ 15 mm, plates with wall thickness ⁇ 10 mm and welding wire with a diameter of 2 mm to 4 mm.
  • the composition or components comprising these is / are weldable, thermoformable and / or bondable.
  • commercially available adhesive resin can be used to reinforce a GRP layer for bonding.
  • a processing temperature of the polyvinyl chloride composition is practically in the same range as in known PVC-U.
  • the polyvinyl chloride composition or components thereof readily the requirements of DIN 8061/62 for pressure pipes.
  • the polyvinyl chloride composition is therefore inexpensive, extremely resistant to chemicals, easy to work with and very stable. It is also compatible with components that include known PVC-U.
  • the chlorine content of the total composition is preferably between 57% to 60%.
  • the molecular weight distribution is preferably determined by gel permeation chromatography (GPC) after separation of the non-tetrahydrofuran (THF) soluble components.
  • the solvent used is THF, preferably at a flow rate of 0.8 mL / min.
  • polystyrene calibration standards are preferably used, preferably an RI detector from Agilent is used.
  • the separation column used is preferably two PSS SDV columns 10 ⁇ 8 x 600 mm.
  • the calibration standards are preferably obtained from PSS Polymer Standards Service GmbH, preferably using the following standards: Lot.- No. M P / Da M N / Da M W / Da Ps 200504 1820 1770 1920 Ps 6126 3470 3260 3460 Ps 24076 10,400 10 000 10,300 Ps 12030 19,600 18,600 19 100 Ps 7122 34,300 33,000 34,000 Ps 1073 67,500 64,000 65,000 Ps 10068 100,000 92,000 96,000 Ps 5070 250,000 236,000 248,000 Ps. 7082 336,000 330,000 335,000 Ps 61120 556,000 536,000 546,000 Ps 2056 824,000 769,000 803,000 Ps. 21036 1 044 000 970,800 1 103 000 Ps 2040 2 470 000 1 810 000 2 010 000
  • the chlorine content of the total composition is preferably determined via a Schöniger digestion with subsequent titrimetric determination of the chlorine content.
  • the PVC composition is preferably free of polypropylene, polyvinylidene fluoride and / or ethylene-chlorotrifluoroethylene.
  • the PVC composition is characterized in that it has a Vicat softening temperature of> 88 ° C, in particular> 90 ° C.
  • the PVC composition is thus versatile, especially in the chemical industry, especially in the chlorine industry, where many processes occur at a temperature of about 60 ° C to about 92 ° C. In many cases it is then no longer necessary to resort to more expensive and ultimately less stable material concepts.
  • the PVC composition of the invention is also characterized by being free of impact modifiers. Most preferably, it is free of added impact modifiers. Accordingly, no impact modifiers are preferably added to the formulation for the PVC composition. This leads to a significantly higher stability, in particular compared with the contact with strongly basic media, because in particular the added impact modifiers are responsible for a susceptibility of known compositions in this respect.
  • a PVC composition characterized by being free of chalk and / or calcium and / or magnesium. It is particularly preferably free of added chalk and / or added calcium and / or added magnesium.
  • the formulation for the composition is / are therefore preferably added no chalk and / or no calcium and / or no magnesium or chalk-containing substances and / or substances comprising calcium and / or substances comprising no magnesium. Since chalk is significantly responsible for acid stability of known materials, the polyvinyl chloride composition has a significantly increased Stability to acids. In the chlorine industry, the lowest possible content of calcium and / or magnesium in components used there is generally required.
  • the PVC composition is therefore particularly suitable for use in the chlorine industry.
  • a PVC composition which is characterized by comprising tin.
  • the PVC composition comprises a component which comprises tin. This may be, for example, an organometallic stabilizer component.
  • stabilization with lead-containing components is preferably avoided, as a result of which the PVC composition is toxicologically harmless.
  • stabilization based on tin or tin-containing components is very efficient.
  • a pipe, a gutter or a container for the passage and / or storage of chemically aggressive substances with the features of claim 4 is provided.
  • These products are characterized by comprising a PVC composition according to one of the previously described embodiments.
  • a PVC composition according to one of the previously described embodiments.
  • the pipe or the gutter is / are preferably used in plant construction, in particular in large-scale chemical plant construction, especially in the chlorine industry. It can be dispensed with a complicated and expensive post-annealing of welds, because the PVC composition is simple and similar Temperature as known PVC-U is processable.
  • a tube which is characterized in that it is designed as a composite tube.
  • the composite tube comprises a sheath comprising glass fiber reinforced thermosetting resin. It also has an inner wall comprising a PVC composition according to any of the embodiments described above. This results in the already mentioned advantages. Moreover, the coefficient of thermal expansion of the PVC composition is less different from a coefficient of thermal expansion of the glass fiber reinforced thermosetting resin than is the case with known composite pipes comprising, for example, polypropylene. As a result, high shear forces are minimized with frequent and in particular abrupt temperature changes, so that the mechanical stress on the composite pipe is lower.
  • a composite tube which is characterized in that the inner wall is connected to the shell by at least one adhesive resin.
  • This type of connection is due the properties of the polyvinyl chloride composition possible. It can therefore be dispensed with a glass fleece, so that the associated problems do not arise.
  • the use of an adhesive resin allows a chemical instead of a mechanical bond, which results in a very high reproducibility of an increased quality standard with regard to an adhesive shear strength of the composite of GRP height and PVC inliner.
  • In the transition region between the shell and the inner wall there is no accelerated progressing corrosion, which in particular could continue rapidly along a longitudinal extent of the pipe. Therefore, damage to the pipe, if any, is locally limited so that the entire pipe system does not fail.
  • the object is also achieved by providing a use of a PVC composition according to claim 7.
  • the PVC composition according to one of the embodiments described above is used according to the invention as a chemical and temperature-resistant material for the production of pipes, gutters, containers, plates, moldings and / or welding wire.
  • the products thus produced are inexpensive, easy to process and extremely resistant to chemicals.
  • the object is also achieved by providing a use of a PVC composition according to claim 8.
  • the PVC composition according to any of the embodiments described above is used as a chemical and temperature resistant material for a pipe, gutter or container according to any one of claims 4 to 6. It is particularly preferably used for producing a so-called liner composite component.
  • This is, for example, a composite pipe which has a GRP shell and a thermoplastic liner, which preferably comprises the PVC composition according to one of the embodiments described above as a chemically resistant inner wall. This results in the already described advantages.
  • a pipe, a gutter or a container according to claim 9.
  • the product according to any of the embodiments described above is used for the passage and / or storage of a chemically aggressive substance comprising at least one component selected from a group consisting of preferably aqueous potassium or sodium hydroxide solution - preferably ⁇ 50% KOH or NaOH -, preferably aqueous potassium chloride solution - preferably with ⁇ 350 g / L KCl -, preferably aqueous sodium chloride solution - preferably with ⁇ 350g / L NaCl -, preferably aqueous hypochlorite solution - preferably with ⁇ 18% active chlorine solution - and a concentrated mineral acid.
  • a chemically aggressive substance comprising at least one component selected from a group consisting of preferably aqueous potassium or sodium hydroxide solution - preferably ⁇ 50% KOH or NaOH -, preferably aqueous potassium chloride solution - preferably with ⁇ 350 g / L KCl
  • the mineral acid preferably comprises concentrated sulfuric acid - preferably ⁇ 120% SO 3 -, concentrated hydrochloric acid ⁇ 37%, concentrated nitric acid ⁇ 68% or concentrated hydrofluoric acid. Since the PVC composition containing the Contains product that is very resistant to chemicals both against acids and alkalis, this can be readily used for the passage and / or storage of aggressive substances or mixtures, in particular of the substances mentioned. This results in the already described advantages.
  • the PVC composition is preferably prepared by gelling or homogenizing various PVC crude resin components together.
  • the various crude resin components have different molecular weights and chlorine contents. More preferably, the various crude resin components are selected so that they can be homogenized or gelled without decomposition of lower melting components, ultimately resulting in a monomodal molecular weight distribution for the PVC resin of the PVC composition.
  • a gelling agent is added, which particularly preferably comprises an acrylate-based gelling agent.
  • the resulting PVC composition clearly exceeds the creep pressure behavior required for a temperature of 80 ° C. according to DIN 8061/62 even at a temperature of 90 ° C. ( FIG. 3 ).
  • the PVC composition it is preferable to dispense with the addition of, in particular, hydrolysis-sensitive and / or oxidation-sensitive lubricants and / or processing aids. This further increases the chemical resistance of the PVC composition. If lubricants and / or processing aids are added, it is preferably ensured that they are as little as possible sensitive to hydrolysis and / or oxidation.
  • the PVC composition is free of calcium stearate, especially free of added calcium stearate. Most preferably, it is completely free of any stearate, especially added stearate.
  • the PVC composition comprises a first PVC resin component which consists of unplastified PVC.
  • the first PVC resin component is through the CAS number 9002-86-2 characterized.
  • the PVC composition further comprises a second resin component which is a polymer having a high chlorine content compared to the first resin component.
  • the second resin component has a molecular weight distribution having a lower number average and a lower weight average than the first resin component.
  • the second resin component is a PVC resin component.
  • the second resin component is through the CAS number 68648-82-8 characterized.
  • the PVC composition comprises more than two resin components.
  • the first PVC resin component has a molecular weight distribution with a weight average M W of 140 kDa to 154 kDa, preferably 141 kDa to 153 kDa, preferably 142 kDa to 152 kDa, preferably 143 kDa to 151 kDa, preferably 144 kDa to 150 kDa 145 kDa to 149 kDa, up.
  • the number average M N of the molecular weight distribution of the first PVC resin component is according to the invention 70 kDa to 77 kDa, preferably 71 kDa to 76 kDa.
  • the chlorine content of the first PVC resin component is preferably 54% to 60%, preferably 55% to 59%, preferably 56% to 58%.
  • the second resin component has a molecular weight distribution with a weight average M w of 101 kDa to 113 kDa, preferably 102 kDa to 112 kDa, preferably 103 kDa to 111 kDa, preferably 104 kDa to 110 kDa, preferably 105 kDa to 109 kDa.
  • the number average M N of the molecular weight distribution of the second PVC resin component is 54 according to the invention kDa to 63 kDa, preferably 55 kDa to 62 kDa, preferably 56 kDa to 61 kDa, preferably 57 kDa to 60 kDa.
  • the chlorine content of the second resin component is preferably 62% to 69%, preferably 63% to 68%, preferably 64% to 67%, preferably 65% to 66%.
  • the PVC composition comprises the first resin component and the second resin component in a ratio of 40:60 to 60:40, preferably 45:55 to 55:45, preferably 48:52 to 52:48.
  • the PVC composition preferably further comprises a tin stabilizer, preferably mono-octyl tin or di-octyl tin or a mixture of mono- and di-octyl tin.
  • the tin stabilizer comprises a compound with the CAS number 15571-58-1 or a connection with the CAS number 27107-89-7 or a mixture of these compounds.
  • the PVC composition preferably has the tin stabilizer in a mass fraction of 0.1 phr to 1 phr, preferably 0.3 phr to 0.8 phr, preferably 0.4 phr to 0.7 phr.
  • the parts per hundred rubber unit used herein means parts per 100 parts total resin of the composition.
  • the PVC composition comprises titanium dioxide, more preferably with the CAS number 13463-67-7 , with a mass fraction of 0.05 phr to 0.4 phr, preferably 0.09 phr to 0.3 phr, preferably 0.1 phr to 0.25 phr.
  • the PVC composition preferably comprises at least one pigment and / or at least one dye, especially preferably selected from the list consisting of compounds with the CAS numbers 6536-46-2, 57455-37-5 and 15782-05-5 , In particular, it is possible to mix several pigments and / or dyes depending on the desired color of the PVC composition.
  • the pigment or dye content of the PVC composition is preferably 0.1 phr to 1.0 phr, preferably 0.4 phr to 0.8 phr, preferably 0.6 phr to 0.7 phr.
  • the PVC composition preferably comprises a first, oxidized polyethylene wax component, preferably based on CAS number 9002-88-4 , preferably with a drop point (Mettler Drop Point, ASTM D-3954) of 101 ° C and an acid number (ASTM D-1386) of 15 mg KOH / g.
  • the first, oxidized polyethylene wax component is preferably present in a mass fraction of 0.5 phr to 1.1 phr, preferably 0.6 phr to 1 phr, preferably 0.65 phr to 0.9 phr.
  • the PVC composition comprises a second, oxidized polyethylene wax component, preferably also based on the CAS number 9002-88-4 , preferably with a drop point (Mettler Drop Point, ASTM D-3954) of 140 ° C and an acid number (ASTM D-1386) of 7 mg KOH / g.
  • the second polyethylene wax component preferably differs from the first polyethylene wax component by the dropping point and the acid number.
  • the mass fraction of the second polyethylene wax component is 0 phr to 0.4 phr, preferably 0.05 phr to 0.2 phr.
  • the PVC composition comprises a Fischer-Tropsch wax component, preferably an unfunctionalized one Fischer-Tropsch hard paraffin with a dropping point (DGF M-III 3) of 108 to 114 ° C and an acid number (DGF M-IV 2) of ⁇ 1 mg KOH / g.
  • a Fischer-Tropsch wax component preferably an unfunctionalized one Fischer-Tropsch hard paraffin with a dropping point (DGF M-III 3) of 108 to 114 ° C and an acid number (DGF M-IV 2) of ⁇ 1 mg KOH / g.
  • the mass fraction of Fischer-Tropsch wax component is 0.3 phr to 0.7 phr, preferably 0.4 phr to 0.6 phr.
  • Essential in the composition of the oxidized polyethylene wax components and the Fischer-Tropsch wax component is that as far as possible no additional functional groups are introduced into the PVC composition, which could adversely affect their chemical stability. It is also essential that conventional additives which comprise calcium, for example calcium stearate, be dispensed with. Overall, it is envisaged that no chemically labile functionalities will be integrated into the composition.
  • oxidized polyethylene wax components and Fischer-Tropsch wax components are preferably matched to the actual machines available for making the PVC composition and the processing conditions.
  • the PVC composition preferably comprises at least one acrylate-based gelling and / or processing aid, particularly preferably with the CAS number 27136-15-8 .
  • the gelling and / or processing aid preferably has a mass fraction of 0.8 phr to 1.2 phr, preferably 0.9 phr to 1.1 phr, preferably 0.95 phr to 1.05 phr, preferably 0.97 phr to 1.03 phr up.
  • the PVC composition preferably comprises at least one antioxidant, more preferably with the CAS number 6683-19-8 ,
  • the antioxidant preferably has a mass fraction of 0.5 phr to 1.4 phr, preferably 0.8 phr to 1.2 phr, preferably 0.9 to 1.1 phr.
  • the PVC composition is preferably free from flow aids, in particular from added flow aids.
  • a preferred embodiment of the PVC composition comprises a first PVC resin component with the CAS number 9002-86-2 to 48 parts. It comprises a second PVC resin component with the CAS number 68648-82-8 to 52 parts. In this case, the proportion of PVC resin components adds up to 100. Thus, all of the parts mentioned here are ultimately based on 100 parts of total resin, ie in phr.
  • the embodiment further comprises a tin stabilizer at 0.5. Share which ingredients with the CAS numbers 15571-58-1 and 27107-89-7 includes. It also includes titanium dioxide with the CAS number 13463-67-7 to 0.1 parts.
  • a first oxidized polyethylene wax component having a drop point (Mettler Drop Point, ASTM D-3954) of 101 ° C and an acid number (ASTM D-1386) of 15 mg KOH / g is comprised of 0.9 parts
  • a second Oxidized polyethylene wax component having a drop point (Mettler Drop Point, ASTM D-3954) of 140 ° C and an acid number (ASTM D-1386) of 7 mg KOH / g is comprised to 0.1 part.
  • the total amount of oxidized polyethylene wax components is thus 1.0 part.
  • the various components of the PVC composition are mixed, gelled or processed in a customary manner and then preferably extruded.
  • DEKADUR Plus refers to a PVC composition according to the preferred embodiment.
  • FIG. 1 shows the tensile strength according to DIN EN ISO 527 of various PVC compositions plotted against the temperature. It shows that the curve marked 33-19-10, which concerns DEKADUR Plus, always lies above the other two curves. In particular, the tensile strength of DEKADUR Plus in the temperature range above 60 ° C is significantly increased compared to the other two materials.
  • the curve indicated by R 33 relates to the formulation PVC-U (troisdorfrot) of Georg Fischer DEKA GmbH, and the 33-7-10 curve relates to a slightly modified prototype formulation based on PVC-U (troisdorfrot) of Georg Fischer DEKA GmbH. Both comparative formulations have a chalk content of ⁇ 3%.
  • FIG. 2 shows the tensile modulus of elasticity according to DIN EN ISO 527 of various compositions plotted against the temperature.
  • DEKADUR Plus has a higher modulus of elasticity than the comparative formulations, especially in the temperature range> 60 ° C.
  • the curve marked PP 2222 relates to a standard polypropylene formulation frequently used in the chlorine industry, in particular for the catholyte cycle. For the description of the other curves and the compositions which concern them, reference is made to the information FIG. 1 directed.
  • FIG. 3 shows the creep internal pressure behavior, namely the hoop stress of DEKADUR Plus plotted against time (square measurement points) compared to the illustrated as a solid line 80 ° C DIN curve for PVC-U according to DIN 8061/62.
  • the measured values for DEKADUR Plus were measured at a temperature of 90 ° C.
  • the measuring point shown as a circle indicates a measurement which was interrupted because at the given hoop voltage a measuring time of a few decades would result. Nevertheless, it turns out that this measuring point is also clearly above the standard curve.
  • the experimentally determined behavior for DEKADUR Plus at a temperature of 90 ° C is also confirmed by extrapolation with pressure increase tests according to the Miner's rule.
  • FIG. 3 It is clear that pipes containing DEKADUR Plus are more resistant to pressure at a temperature of 90 ° C than required by the standard DIN 8061/62 for a temperature of 80 ° C.
  • the chemical resistance behavior of DEKADUR Plus is determined by the experimental results shown in the following tables Data confirmed.
  • immersion experiments with media contact were made from all sides of the samples used.
  • the sample material used was extruded tubes with an outer diameter of 63 mm and a wall thickness of 4.7 mm.
  • PVC-U 1 denotes the recipe PVC-U (troisdorfrot) Georg Fischer DEKA GmbH, which includes a lead stabilizer.
  • PVC-U 2 designates a prototype formulation of Georg Fischer DEKA GmbH based on PVC-U (troisdorfrot), wherein a tin stabilizer is included instead of the lead stabilizer.
  • Both formulas PVC-U 1 and PVC-U 2 contain less than 3% chalk.
  • Other standard PVC-U formulations have a chalk content of about 6%.
  • the formulations PVC-U 1 and PVC-U 2 in terms of their resistance to chemicals already improved over other standard formulations.
  • PVC-C refers to the recipe DEKADUR C of Georg Fischer DEKA GmbH based on the raw material Temprite 88708 in connection with the following tables.
  • Table 1 recipe Weight change /% Penetration depth / ⁇ m (inside / outside) Change Vicat / K Blistering / deformation
  • PVC-U 1 11.1 610/520 4.4 Yes DEKADUR Plus 7.8 550/480 0.9 No
  • Table 2 shows an experiment in which the samples in a field trial for seven months in a bypass of a paper mill bleach chlorine dioxide with 1% ClO 2 with a solid content (pulp content - substantially wood shares) of 5% at a temperature of 68 ° C were exposed to 75 ° C.
  • the formulation which is given as "PVC-U with 7 phr acrylate-based impact modifier", is based on a standard PVC-U recipe which additionally 7 phr acrylate-based impact modifier was added.
  • the formulations PVC-U 1 and PVC-U 2 are free of impact modifiers.
  • PVC-U with Stabilizer and Antioxidant Package from DEKADUR Plus is a standard PVC-U formulation to which stabilizer and antioxidant components have been added as in DEKADUR Plus.
  • the tests referred to in Table 2 were performed to demonstrate the impact of an impact modifier on the chemical resistance of a PVC-U formulation and to demonstrate the clear superiority of the stabilizers and antioxidants selected for the DEKADUR Plus formulation.
  • the values given in Table 2 clearly show the negative influence of the impact modifier, in particular on the penetration depth.
  • the formulation with the stabilizers and antioxidants from DEKADUR Plus has significantly improved properties.
  • Table 3 ⁇ / b> recipe Weight change /% Penetration depth / ⁇ m (inside) PVC-U 1 0.45 258 PVC-U 2 0.78 460 DEKADUR Plus 0.30 183
  • Table 3 relates to the chemical resistance of various samples to nitric acid.
  • the samples were exposed to nitric acid with 55% HNO 3 at a temperature of 60 ° C for a period of eight weeks.
  • the values given in Table 3 clearly show the distinct advantages in the chemical resistance of DEKADUR Plus compared to PVC-U 1 and PVC-U 2 compared to oxidizing mineral acids such as concentrated nitric acid.
  • Table 4 ⁇ / b> recipe Weight change /% Penetration depth Blackening by SO 3 PVC-U 1 0.19 entire sample volume interspersed DEKADUR Plus 0.57 only surface
  • Table 4 relates to the chemical resistance of DEKADUR Plus compared to PVC-U 1 versus concentrated sulfuric acid where the samples were exposed to concentrated sulfuric acid (96%) for three weeks at a temperature of 90 ° C.
  • the values in Table 4 clearly show the completely different and improved corrosion behavior of DEKADUR Plus.
  • the diffusion of SO 3 in DEKADUR Plus is significantly delayed.
  • Table 5 ⁇ / b> recipe Weight change /% Penetration depth Blackening by SO 3 PVC-U 1 1.38 strong diffusion with blackening DEKADUR Plus 1.22 only surface DEKADUR Plus 4h / 95 ° C annealed 0.98 only surface
  • Table 5 relates to the chemical resistance of two DEKADUR Plus samples compared to PVC-U 1 versus sulfur trioxide.
  • the second DEKADUR Plus sample differs from the first one in that it was annealed at 95 ° C for four hours. The samples were exposed to a saturated SO 3 atmosphere in the gas phase over 20% oleum at 20 ° C for two weeks.
  • the values of Table 5 show that the corrosion behavior of DEKADUR Plus is significantly different and opposite for both samples PVC-U 1 is improved. In particular, the diffusion of SO 3 in DEKADUR Plus is significantly delayed. Annealing the DEKADUR Plus sample further increases its durability.
  • Table 6 relates to changes in the properties of various material samples in the table compared to concentrated sodium hydroxide (32%) at a temperature of 95 ° C, compared to the data of a blank sample, ie a freshly prepared, not exposed to the chemical sample.
  • Various changes in properties are shown as a function of a storage time in weeks for the different samples in the liquor. These are the mass change, a change in color, the penetration depth, the change in the Vicat softening temperature, the change in modulus of elasticity, the change in tensile strength and the change in elongation at break.
  • Table 7 relates to an experiment in which the samples were exposed to three or eight weeks of concentrated hydrochloric acid (35%) at 60 ° C, respectively. Indicated are the weight change and the penetration depth (inside) for the respective storage time.
  • DEKADUR Plus has improved properties compared to PVC-U 1 and PVC-U 2.
  • DEKADUR Plus shows a significantly lower absorption of hydrochloric acid. This feature has great advantages in using tubes that include DEKADUR Plus as a liner. The lower uptake / sorption due to lesser reaction with hydrochloric acid is combined with an accelerated diffusion, so that the penetration depth of DEKADUR Plus is increased.
  • Table 8 relates to an experiment in which the samples of concentrated hydrofluoric acid (40%) were exposed at 40 ° C for three weeks.
  • the values from Table 8 show that PVC-C absorbs hydrofluoric acid to a very high degree by reaction with constituents of the formulation. This results in a delayed diffusion, ie a lower penetration depth.
  • DEKADUR Plus shows a very good compromise in behavior with respect to hydrofluoric acid and other acids, whereby the permeation behavior of DEKADUR Plus essentially corresponds to that of PVC-U and thus clearly distinguishes itself from PVC-C in particular.
  • the catholyte circuit in a chlorine electrolysis plant is likewise a suitable field of application for the PVC composition or components which comprise it.
  • PVC composition or components which comprise it.
  • about 30% to about 50% potassium or sodium hydroxide solution accumulates at a temperature of about 85 ° C to about 92 ° C.
  • Use of standard PVC-U is eliminated for thermal reasons.
  • PVC-C is not a suitable material because of its lye instability. In connection with composite materials made of PP / GRP, the already mentioned disadvantages arise.
  • the PVC composition and products comprising them offer the advantage of cost-effective production, ease of processing, and optimum chemical and temperature resistance.
  • a use in the sodium hypochlorite production for example in chlorine killers of chlorine plants, as well as other applications in connection with sodium hypochlorite, preferably at a temperature of ⁇ 60 ° C at.
  • Sodium hypochlorite is usually stabilized alkaline. It is often produced by the introduction of chlorine gas into a sodium hydroxide solution. Therefore, it is hardly possible to resort to materials that comprise PVC-C, because this excretes because of its already described base lability. The maximum temperatures, especially for chlorine killer units, are unacceptable for materials comprising standard PVC-U. Polyolefins are not stable at the conditions prevailing in this range. Also here, therefore, offers the polyvinyl chloride composition or a product which this covers, a cost-effective solution for an application field, which places high demands on the materials used.
  • thermoplastic inliner it is also possible to use the PVC composition or a product comprising it for the production of oxygen supply lines, where a flame-retardant behavior of a thermoplastic inliner is required.
  • expensive pipes can be replaced or avoided, which include polyvinylidene fluoride (PVDF) as inliner material and a GRP shell.
  • PVDF polyvinylidene fluoride
  • polyvinyl chloride composition for the production of lines, pipes, channels and / or tanks for concentrated sulfuric acid of> 90%, especially at higher and especially at fluctuating temperature.
  • materials can be replaced or avoided, which include expensive ethylene-chlorotrifluoroethylene and / or fully fluorinated plastics.
  • the polyvinyl chloride composition is particularly resistant to acids, anolyte in the chlorine electrolysis, wet chlorine, hypochlorite, brines, alkalis and / or concentrated sulfuric acid even at high application temperatures that are no longer achievable for conventional PVC-U.
  • the PVC composition Due to their low thermal expansion compared to polyolefin compositions, the PVC composition is less sensitive to temperature fluctuations.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP12000194.6A 2012-01-13 2012-01-13 Polyvinylchlorid-Zusammensetzung, Rohr, Rinne oder Behälter, Verwendung einer PVC-Zusammensetzung und Verwendung eines Rohrs, einer Rinne oder eines Behälters Active EP2615137B2 (de)

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EP12000194.6A EP2615137B2 (de) 2012-01-13 2012-01-13 Polyvinylchlorid-Zusammensetzung, Rohr, Rinne oder Behälter, Verwendung einer PVC-Zusammensetzung und Verwendung eines Rohrs, einer Rinne oder eines Behälters
JP2014551579A JP6253594B2 (ja) 2012-01-13 2013-01-04 管、ダクト、容器、板、成形部材または溶接棒の製造のためのポリ塩化ビニル（ｐｖｃ）組成物、当該ｐｖｃ組成物を含む管、ダクトまたは容器、あるいは、当該ｐｖｃ組成物、管、ダクトまたは容器の使用
RU2014121333A RU2621109C2 (ru) 2012-01-13 2013-01-04 Композиция на основе поливинилхлорида, труба, канал или контейнер, применение композиции пвх и применение трубы, канала или контейнера
CN201380005272.4A CN104169360A (zh) 2012-01-13 2013-01-04 聚氯乙烯 - 组合物、管、槽或容器，pvc组合物的用途和管、槽或容器的用途
AU2013209093A AU2013209093B2 (en) 2012-01-13 2013-01-04 Polyvinyl chloride - composition, tube, channel or container, use of a PVC composition and use of a tube, of a channel or of a container
IN1093KON2014 IN2014KN01093A (zh) 2012-01-13 2013-01-04
PCT/EP2013/050081 WO2013104562A1 (de) 2012-01-13 2013-01-04 Polyvinylchlorid-zusammensetzung, rohr, rinne oder behälter, verwendung einer pvc- zusammensetzung und verwendung eines rohrs, einer rinne oder eines behälters
US14/371,104 US20150000782A1 (en) 2012-01-13 2013-01-04 Polyvinyl chloride - composition, tube, channel or container, use of a pvc composition and use of a tube, of a channel or of a container
BR112014016177-1A BR112014016177B1 (pt) 2012-01-13 2013-01-04 composição de policloreto de vinila e seus usos, tubo, canal ou recipiente e seu uso

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RU2630797C2 (ru) * 2012-02-15 2017-09-13 Басф Се Композиции пвх, обладающие высокой ударопрочностью
JP6498954B2 (ja) * 2015-02-12 2019-04-10 リケンテクノス株式会社 塩化ビニル系樹脂組成物
JP6498953B2 (ja) * 2015-02-12 2019-04-10 リケンテクノス株式会社 塩化ビニル系樹脂組成物
JP2020186806A (ja) * 2019-05-17 2020-11-19 積水化学工業株式会社 耐熱透明継手
KR102238259B1 (ko) * 2020-12-02 2021-04-09 (주) 삼정디씨피 상하수도관용 pvc 파이프 제조방법
KR102238260B1 (ko) * 2020-12-02 2021-04-09 (주) 삼정디씨피 이중벽 하수관용 pvc 파이프 제조방법

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EP2615137B1 (de) 2015-10-07
WO2013104562A1 (de) 2013-07-18
AU2013209093A1 (en) 2014-06-05
JP6253594B2 (ja) 2017-12-27
US20150000782A1 (en) 2015-01-01
IN2014KN01093A (zh) 2015-10-09
RU2621109C2 (ru) 2017-05-31
EP2615137A1 (de) 2013-07-17
BR112014016177B1 (pt) 2021-02-09
AU2013209093B2 (en) 2015-04-09
CN104169360A (zh) 2014-11-26
BR112014016177A8 (pt) 2017-07-04
JP2015511248A (ja) 2015-04-16
RU2014121333A (ru) 2016-03-10

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